US2743262A - A-(chloroacetamido)-acrylic esters and their homo- and co-polymers - Google Patents
A-(chloroacetamido)-acrylic esters and their homo- and co-polymers Download PDFInfo
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- US2743262A US2743262A US298458A US29845852A US2743262A US 2743262 A US2743262 A US 2743262A US 298458 A US298458 A US 298458A US 29845852 A US29845852 A US 29845852A US 2743262 A US2743262 A US 2743262A
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- chloroacetamido
- methyl
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- acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
Definitions
- a-(chloroacetamido)-acrylic esters can be readily prepared by treating the silver salt of a-(chloroacetamido) -acrylic acid with an alkyl iodide or by saturating an alcoholic solution of a-(chloroacetamido)- acrylic acid with dry hydrogen chloride.
- the esters are purified by distillation under reduced pressure.
- a-(Chloroacetamido)-acrylic acid is obtained from the reaction of pyruvic acid and chloroacetamide as shown by Bergman and Grafe (Z. Physiol. Chem. 187, 187 (1930)), The other product of this reaction, a,a-bis- (chloroacetamido)-propionic acid can be heated in acetic acid solution to split out one molecule of chloroacetamide and form more of the a-(chloroacetamido)-acrylic acid.
- the a-(chloroacetamido)-acrylates readily homopolymerize and copolymerize to mers which can be used, for example, as molding materials
- the usual catalyst or initiating agents such as hydrogen peroxide, benzoyl peroxide, potassium persulfate, Porophor-N, and so forth are used and certain activating agents such as sodium bisulfite may be used with the usual catalysts.
- a percent by weight copolymer of methyl a-(chloroacetamido)-acrylate with acrylonitrile has a softening point above 180 C. and can be spun into fibers which have excellent dyeing properties.
- a further object resides in the provision of homopolymers and copolymers of a-(chloroacetamido)-acrylic acid esters.
- Another object resides in the provision of a method of preparing these esters.
- Example 2 --Ethyl a-(chloroacetamido)'acrylate Dry hydrogen chloride was admitted with stirring into a chilled suspension of 10, g. of a-chloroacetamidoacry1ic acid in cc. of absolute ethanol. Stirring and cooling were continued for one hour after the mixture became saturated with hydrogen chloride. The solid dissolved. After removal of a portion "of the ethanol and hydrogen chloride under reduced pressure, sodium ethoxide. was pH of the mixture up. to 6. .Sodium chloride was removed by filtration. Hydroquinone, 0.05 g., was added to the filtrate and. the. product was collected by distillation, at 7 8-80 C./0.1 mm.
- Example 4 Five grams of methyl a-(chloroacetamido)-acrylate was C. in a nitrogen atmosphere using 0.1 percent acetyl peroxide as a catalyst. The product is a clear, hard, moldable polymer.
- Example 5 Example 6 1 moldable polymer formed.
- Example 8 Two grams of methyl a-(chloroacetamido )-acrylate and eight grams of methyl methacrylate were copolymerized at 60 C. using 0.1 percent acetyl peroxide catalyst. The product is a clear, hard, moldable polymer.
- Example 9 Eight grams of styrene and two grams of ethyl a-(chloroacetamidoyacrylate were copolymerized at 60 C. using 0.1 percent acetyl peroxide as a catalyst to form a clear, hard, moldable polymer.
- Example 10 Five grams of acrylonitrile, 1.0 g. of methyl a-(chloroacetamido)-acrylate, 0.055 g. of ammonium pet-sulfate and 0.1 g. of sodium bisulfite were placed in 45 cc. of distilled water. The polymerization began immediately and was complete after several hours at 50 C. The white polymer was filtered, washed and dried. The polymer is soluble in dimethyl formamide and dimethyl acetamide.
- Example 12 Two grams of methyl a-(chloroacetamido)-acrylate, 7 g. of vinyl chloride, 1 g. of soap, 0.05 g. of ammonium persulfate and 0.1 g. of ammonium bisulfite were added to ILTHC 0 0 H201 where R is an alkyl group of 1-3 carbon atoms.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
i or fibers.
A- cntonoxcurxivnnm-xcnvuc ESTERSAND 111mm HM01 AND (1.0-POLYMERS Harry W. Coover, J12, and Newton 11. Shearer, Ira, Kiugsport, Tenn., assignors to EastmanKodak Company,
Rochester, N. Y., a corporation of New Jersey No Drawing. Application July 11, 1952, SerialNo- 223,458 s 14 Claims. (Cl. 2 0-855 This invention relates to new and valuable esters of a-(chloroacetamido)-acrylic: acid andtheir homopolymers 1 and copolymers. The monomers have the formula:
CHFC C 03R Nrtoocmcl isopropyl, etc.
1 The homopolymers and copolymers of-the invention possess outstanding valuable properties to an unexpected degree, particularly in their unusually high softening points. i
We have found that the a-(chloroacetamido)-acrylic esters can be readily prepared by treating the silver salt of a-(chloroacetamido) -acrylic acid with an alkyl iodide or by saturating an alcoholic solution of a-(chloroacetamido)- acrylic acid with dry hydrogen chloride. The esters are purified by distillation under reduced pressure.
a-(Chloroacetamido)-acrylic acid is obtained from the reaction of pyruvic acid and chloroacetamide as shown by Bergman and Grafe (Z. Physiol. Chem. 187, 187 (1930)), The other product of this reaction, a,a-bis- (chloroacetamido)-propionic acid can be heated in acetic acid solution to split out one molecule of chloroacetamide and form more of the a-(chloroacetamido)-acrylic acid.
The a-(chloroacetamido)-acrylates readily homopolymerize and copolymerize to mers which can be used, for example, as molding materials The usual catalyst or initiating agents such as hydrogen peroxide, benzoyl peroxide, potassium persulfate, Porophor-N, and so forth are used and certain activating agents such as sodium bisulfite may be used with the usual catalysts.
As an example of the valuable properties imparted to polymers, a percent by weight copolymer of methyl a-(chloroacetamido)-acrylate with acrylonitrile has a softening point above 180 C. and can be spun into fibers which have excellent dyeing properties.
It is an object of our invention to provide new compounds comprising the a-(chloroacetamido)-acrylic acid esters. A further object resides in the provision of homopolymers and copolymers of a-(chloroacetamido)-acrylic acid esters. Another object resides in the provision of a method of preparing these esters.
The following examples will illustrate the invention, but they are to be considered in an illustrative and not a limiting sense.
PREPARATION OF THE MONOMERS Example 1 .-M ethyl a-(chloroacetamido) -acrylate give new and valuable polyadded to bring the 20 where R is an alkyl group such as methyl, ethyl, propyl,
. polymerized at 60 2,743,262 Patented Apr. 24, 1956 iodide containing 0.1 g. of hydroquinone. The exothermic reaction caused warming of themethyl iodide to reflux. The mixture was stirred for one half hour at room temperature; then filtered. The filtrate was distilled through a short unpacked column. The methyl a(chloroacetamido)-acrylate was collected at 67-69 C./0.08 mm. and solidified upon cooling in the receiver.
Example 2.--Ethyl a-(chloroacetamido)'acrylate Dry hydrogen chloride was admitted with stirring into a chilled suspension of 10, g. of a-chloroacetamidoacry1ic acid in cc. of absolute ethanol. Stirring and cooling were continued for one hour after the mixture became saturated with hydrogen chloride. The solid dissolved. After removal of a portion "of the ethanol and hydrogen chloride under reduced pressure, sodium ethoxide. was pH of the mixture up. to 6. .Sodium chloride was removed by filtration. Hydroquinone, 0.05 g., was added to the filtrate and. the. product was collected by distillation, at 7 8-80 C./0.1 mm.
Example 3.-Is0pr0pyl a-(chloroacetamido)-acrylate HOMOPOLYMERIZATION Example 4 Five grams of methyl a-(chloroacetamido)-acrylate was C. in a nitrogen atmosphere using 0.1 percent acetyl peroxide as a catalyst. The product is a clear, hard, moldable polymer.
Example 5 Example 6 1 moldable polymer formed.
COPOLYMERIZATION Example 7 Right grams of methyl a-(chloroacetamido)-acrylate and two grams of methyl methacrylate were copolymerized at 60 C. using 0.1 percent benzoyl peroxide as a catalyst to form a clear, hard, moldable polymer.
Example 8 Two grams of methyl a-(chloroacetamido )-acrylate and eight grams of methyl methacrylate were copolymerized at 60 C. using 0.1 percent acetyl peroxide catalyst. The product is a clear, hard, moldable polymer.
Example 9 Eight grams of styrene and two grams of ethyl a-(chloroacetamidoyacrylate were copolymerized at 60 C. using 0.1 percent acetyl peroxide as a catalyst to form a clear, hard, moldable polymer.
Example 10 3 Example 11 Five grams of acrylonitrile, 1.0 g. of methyl a-(chloroacetamido)-acrylate, 0.055 g. of ammonium pet-sulfate and 0.1 g. of sodium bisulfite were placed in 45 cc. of distilled water. The polymerization began immediately and was complete after several hours at 50 C. The white polymer was filtered, washed and dried. The polymer is soluble in dimethyl formamide and dimethyl acetamide.
Example 12 Two grams of methyl a-(chloroacetamido)-acrylate, 7 g. of vinyl chloride, 1 g. of soap, 0.05 g. of ammonium persulfate and 0.1 g. of ammonium bisulfite were added to ILTHC 0 0 H201 where R is an alkyl group of 1-3 carbon atoms.
2. Methyl a-chloroacetamidoacrylate. 3. Ethyl a-chloroacetamidoacrylate. 4. Isopropyl a-chloroacetamidoacrylate. 5. Homopolymers of the compounds of claim 1.
6. Homopolymeric methyl a-chloroacetamidoacrylate.
7. Homopolymeric ethyl a-chloroacetamidoacrylate.
8. Homopolymeric isopropyl a-chloroacetamidoacrylate.
9. Copolymers of the compounds of claim 1 with a compound selected from the group consisting of methyl methacrylate, styrene, vinyl acetate, acrylonitrile and vinyl chloride. t
10. Copolymers of the compounds of claim 1 with methacrylate.
'11. Copolymers of the compounds of claim 1 with styrene.
12. Copolymers of the compounds of claim 1 with vinyl acetate.
13. Copolymers of the compounds of claim 1 with acrylonitrile.
14. Copolymers of the compounds of claim 1 with vinyl chloride. I
References Cited in the tile of this patent UNITED STATES PATENTS Coover et a1 Apr. 10, 1951 Dickey et a1 Mar. 11, 1952 OTHER REFERENCES 2. Physiol. Chem. 1930 vol. 24,
Claims (2)
1. COMPOUNDS OF THE STRUCTURE
10. COPOLYMERS OF THE COMPOUNDS OF CLAIM 1 WITH METHACRYLATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US298458A US2743262A (en) | 1952-07-11 | 1952-07-11 | A-(chloroacetamido)-acrylic esters and their homo- and co-polymers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US298458A US2743262A (en) | 1952-07-11 | 1952-07-11 | A-(chloroacetamido)-acrylic esters and their homo- and co-polymers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2743262A true US2743262A (en) | 1956-04-24 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US298458A Expired - Lifetime US2743262A (en) | 1952-07-11 | 1952-07-11 | A-(chloroacetamido)-acrylic esters and their homo- and co-polymers |
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| Country | Link |
|---|---|
| US (1) | US2743262A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4361439A (en) * | 1981-08-26 | 1982-11-30 | Stauffer Chemical Company | Method of increasing the yield of legumes utilizing chloroacetyl-aminoacid ethyl esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2548518A (en) * | 1949-04-13 | 1951-04-10 | Eastman Kodak Co | Esters of alpha-acetaminoacrylic acid |
| US2588969A (en) * | 1949-11-26 | 1952-03-11 | Eastman Kodak Co | Certain acylamino-acrylates and-crotonates as insecticides |
-
1952
- 1952-07-11 US US298458A patent/US2743262A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2548518A (en) * | 1949-04-13 | 1951-04-10 | Eastman Kodak Co | Esters of alpha-acetaminoacrylic acid |
| US2588969A (en) * | 1949-11-26 | 1952-03-11 | Eastman Kodak Co | Certain acylamino-acrylates and-crotonates as insecticides |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4361439A (en) * | 1981-08-26 | 1982-11-30 | Stauffer Chemical Company | Method of increasing the yield of legumes utilizing chloroacetyl-aminoacid ethyl esters |
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